Thin film approaches are powerful methods for gaining a nanoscale understanding of interfacial ionic liquids (ILs) in the vicinity of solids. These approaches are used to directly elucidate the interfacial contributions to the physical properties of ILs as nanoscale thin films have significant proportions of the surface or interface region with respect to their total volume. Here, we report the growth of a uniform [emim][TFSA] thin film ionic liquid on a chemically modified, well-wettable sapphire, thereby allowing the in situ measurement of its ionic conductivity on the nanoscale. We observed the thickness-dependent behavior of the ionic conductivity, which gradually decreased especially when the thickness was less than 10 nm, and found it to be quantitatively analyzed well by using an empirical two-layer model. The molecular dynamics (MD) simulations show that the thicknessdependent ionic conductivity originates from the solid-like structuring of the IL near the substrate, reproducing a thickness-dependent ionic conductivity. The MD simulation results suggest that the thickness of the low conductivity region determined in the two-layer model should roughly correspond to the thickness of the solid-like structuring of the IL near the substrate.
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